Alkylation process



Reissued Mar. 21, 1 944 IIUNITED STATES PATENT OFFICE ALKYLATION PROCESS Arlie A. O'Kelly, Woodbury, N. 8.. and Robert H.

Work, Philadelphia, Pa., assignors to Socony- Vacuum Oil Company, Incorporated, New York,

. Y., a corporation of New York No Drawing. Original No. 2,315,129 dated March 30, 1943, Serial No. 356,188, September 10, 191.. Application for reissue October 8, 1943, Serial 6 Claims. (Cl. zoo-683.4)

This invention relates to the alkylation of paramnic hydrocarbons with oleflnic hydrocarbons.

The invention is concerned particularly with the.

manufacture of high octane gasclines by the catalytic alkylation of normally gaseous parafllns with normally gaseous olefins.

Beveral processes have been developed recently for the alkylation of parafllns with oleflns. For the most part these processes have made use of some particular alkylation catalyst. For instance, suliuric acid and aluminum chloride-have been used attlow temperatures. Phosphoric acid has been used at higher temepartures. Again OKelly et al., in the co-pending application Serial No. 324,085, filed March 15, 1940, have dls-.

closed certain metal chlorides and fluorides as alkylation catalysts at high temperatures and pressures.

It is an object of our invention to improve the eiilciency o1 catalytic alkylation processes. A more specific object is to improve the efliciency of catalytic alkylation processes for manufacturing high octane gasoline by alkylating normally gaseous paramns with normally gaseous oleflns.

According to our invention, we alkylate paraflins with oleflns in the presence or an alkylation catalyst and a hydrogenation catalyst that is active under the same conditions as the alkylation catalyst.

Hydrogenation is a well established art. For this reason catalysts that bring about hydrogenation are well known as-alsoare the conditions under which each is most ell'ective. Numerous hydrogenation catalysts may be mentioned by way of example, as, for instance, metal oxides, such as the oxides oi molybdenum, cobalt, chromium, iron, copper, etc.; metal sulfides, as, for example, molybdenum sulfide; and various metalsthemselves such as molybdenum, copper; co

halt, chromium, etc.

While, as is obvious, our invention has a wider application, we prefer to use alkylation catalysts of thejwpe disclosed in O'Kelly etaL, application Serial No. 324.085, namely, metal chlorides or fluorides which are solid, stable compounds at temperatures above about 600 F., and pressures above about 2000 pounds per square inch, with product may be obtained than by using only the special preference being given to such chlorides or-fluorides oi the alkaline earth metals. An outstanding feature of alkylation processes using isoparailins maybealkylated.

' such-catalysts is thateither normal parafflns or In iir paring a combination catalyst for the process oi the present invention, we select a desired alkylation catalyst and then associate ther alkylation catalyst at the same temperature,,or a lower temperature may be used in our process to obtain the same yield as is obtained with an alkylation catalyst alone.

While we do not wish to be held to any particular theory, it is believed the increased eiliciency obtained by our process is due to the similarity between an alkylation reaction and a hydrogenation reaction. This similarity is shown in the following reactions where R represents an alkyl (1) H H 11 H 1 h dmgenltio n-n n-t=t:-H y n H-l-(J-H It will be seenirom the equations that in the hydrogenation reaction both constituents bein added to the olefin at the double bond are hydrogen atoms, while in thealkylation reaction one constituent is a hydrogen atom and the other an alkylradical, I

As'indicatedabove, we particularly prefer certain metal chlorides or fluorides as alkylation catalysts, and such a catalyst is fluorsper. Chromium oxide is a wellknown hydrogenation catalyst which is active under substantially the same condition as fluorspar. Accordingly. a prei erred combination catalyst for the present invention comprises fluorspar plus chromium oxide. Catalystsotthlstypemaybeusedalsoinconnection with "inert carriers ior added support. if desired;

Suitable carriers comprise alumina. bauxite, ZnO,

MgO, etc. In using a catalyst or this type we recommend temperaturesabove about 800 F.,

preferably from about 800 F. to about 900' F., and a pressure above about 2000 lbs. per Sq. in.

In order to illustrate our invention further, we set forth below typical comparative data showing the increased efllciency resulting from the use oi the combination of an alkylation and a hydro- ,genation catalyst rather than the same alkylation catalyst aloneor using only thermal alkylation.

'resultantly higher specific gravity. This is due to a preponderance of polymerization reactions leading to heavier olefin formation.

The predominance of polymerization in the non-catalytic process and o! alkylation in the Re Roaction action Reaction Run 3 Catalyst used and per temp. time reain No in cent by wt. with re ininbags:

m specttocharge sq. gauge F. Mics.

K 1-., l5 Nune 800 30 2,800 I"... 15 -d B50 30 3,100 3..- 16 Elnora-egg boasted) 950 875 30 3. 330

o r 4.-...- 16 Fine heatcdatl000 875 30 3,425

r. 1% hrs. us 2% V Cl: 5(1) 6.. l5 Flglo7rpar+2% Ono; 850 30 3,100

o 6 15 Fluorspar+2% CnOa 826 30 3,825

(17%). '7. 15 do B00 30 3,050 8 l5 Fluors ar+10% Ono; 825 30 3,300

. p 9"--- Fluor|par+Al|0i+2%' 825 2,750

' Percentvol. Specific I odineNo BunNm' fi gr 8 oi'25-100C $3 traction m cases obtained by our process over that given by only an alkylation catalyst (see run 8) We claim:

1. The process 'of alkylating parafllns with oleflns which comprises contacting a mixture consisting substantially oi paramns and oleflns under alkylating conditions with an alkylation 7 catalyst and a hydrogenation catalyst that has appreciable hydrogenation activity at said alkylating conditions.

2. The process ofimanufacturing high octane 1 motor fuel which comprises contacting a mixture consisting substantially of normally gaseous ole-'- flns and normally gaseous parafllns under alkylating conditions with an alkylation catalyst and a hydrogenation catalystthat has appreciable hydrogenation activity at said alkylating conditions.

3. The process of manufacturing high octane motor fuel which comprises contacting a mixture consisting substantiallyof low-boiling paraifins and olefins under alkylating conditions with an alkylation catalyst selected from the group consisting of alkaline earth metal chlorides and fluorides and a hydrogenation catalyst that has appreciable hydrogenation activity under said alkylating conditions.

4. The process of manufacturing high octane motor fuel which comprises contacting a mixture consisting substantially of normally gaseous oleflns'and parafflns at a temperature above about 800 F. and a pressure above about 2000 pounds per square inch with an alkylation catalyst selected i'rom the group consisting of alkaline earth metal chlorides and fluorides and a hydrogenation catalyst that has appreciable hydrogenation activity under said temperature and pressure conditions.

- 900 F. and under a pressure above about 2000 catalytic process is iurther attested to by the dii- .ference in yield of product per pass, since it .is

I hardly likely, for example, that a charge of parts butylene and 680 parts butane (liquid charge) would yield 200 parts of prod ct it only polymerization occurred (see run 4). I also will noted thatvadeflnite improvement in yield is pounds per square inch with an alkylation cata-- lyst selected from the group consisting of alkaline earth metal chlorides and fluorides and a chromic oxide hydrogenation catalyst.

Arum A; OKELLY. ROBERT H. woax. 

